N n&#39;-bis(isomaleimide) polyhydrazides

ABSTRACT

HIGH MOLECULAR WEIGHT POLYHYDRAZIDES HAVE BEEN PREPARED SUCCESSFULLY BY ALLOWING EQUIMOLAR AMOUNTS OF N,N&#39;&#39;-BIS(ISOMALEIMIDE) AND DIHYDRAZIDES TO REACT IN A HIGHLY POPLAR SOLVENT AT ROOM TEMPERATURE. BOTH ALIPHATIC AND AROMATIC POLYHYDRAZIDES ARE AMOROPHOUS RESINS WITH GLASS TRANSITION TEMPERATURES ABOUT 100*C. THEY EXHIBIT EXCELLENT OXYGEN BARRIER PROPERTIES, VERY HIGH DIELECTRIC CONSTANTS AND FAIRLY GOOD MECHANICAL PROPERTIES.

United States Patent "Ce 3,631,005

Patented Dec. 28, 1971 3,631,005 0 0 O 0 f "I N,N'-BIS(lSOMALElMIDE) POLYHYDRAZIDES NHNH LR CNHNHE lLNHNHJi You-Ling Fan, East Brunswick, N.J., assignor to Union L H J Carbide Corporation, New York, N.Y. D

No Drawing. Filed Jan. 29, 1969, Ser. No. 795,075 5 where R and n are as defined above.

8 20/20 Suitable polar solvents which can be used in this class 260-73 UA 3 Clalms of polymerizations include dimethyl sulfoxide, hexamethyl phosphoamide, dimethyl formamide, dimethyl acetamide and the like. Temperature and time are not ABSTRACT OF THE DISCLOSURE 10 narrowly critical although temperatures of about 0 to High molecular Weight polyhydrazides have been 80 C. fand (polymerization times of about 4 to 70 hours pared successfully by allowing equimolar amounts of are Pre erre N,N-bis(isomaleimide) and dihydrazides to react in a Another l P f highly polar solvent at room temperature. Both aliphatic zldes of thls mventlon are normally Solid hnear hlgh and aromatic polyhydrazides are amorphous resins with Polymers obtained by the low e perature solution conglass transition temperatures about 100 C. They exhibit densfmon polymerlzafionpf 'b1(1Sma1e1m1de)d1hY excellent oxygen barrier properties, Very high dielectric drazide adducts and a dlacyl chloride. The adducts are constants and fairly good mechanical properties. Prepared m 1 111916 of NNl'bisfisomaleimide) and 2 moles of a dihydrazlde as delineated below: 0 O This invention relates to the preparation of N,N'-bisit P, (isomaleimide) polyhydrazides and more particularly to 0 0 copolymers of N,N'-bis(isomaleimide) and dihydrazides l O 0 F Q and copolymers of N,N'-bis(isomaleimide), dihydrazides H 6H and diacyl halides. 0= =0 T) (I) o o o p o 0 H,NHNo-R-oNHNH-ii i JNHNHii (iNHNHii-R-iiNHNH,

These polyhydrazides have repeating units represented where R, R" and n are as defined above. by the formula: The preferred solvent system used to carry out this class L\ the]. the.

1 11 wherein each of R, R and R" is a divalent hydrocarbon radical selected from the group consisting of alkylene radicals having 1 to about 18 carbon atoms and arylene iiif ii fifi ifit egir iaiifii a alii ii oiiiif tfifi 23 9 pslrmerizafioa is NN'dimethylaqetamide c integer denoting the degree of polymerization and is sutfimg hthnim dmmde' An amount of i ch10nde.was ciently large so as to afford a normally solid polymer. used .Whlch filflords a molar ratiohwlth the dlcyl Where R is alkylene the preferred dihydrazide is that chlondeiAlt qugh lower mlewlar welg tpolyhydiazldis derived from sebacic acid although those derived from are.obtalned hthlilm chloride? cal} be replficed by ahpheitlc other aliphatic dibasic acids such as oxalic, malonic sucamines Such i meihylene dlamm? P trusopropyl ti cinic, glutaric, adipic, pimelic, suberic, azelaic, dodecanoic, or an ammatlc .amme Such as i Oiher condltlons octadecanoic acids and the like can be used if desired. prifelired for thls class of polymenzatlons Hiclude Polym- Where R is arylene the preferred dihydrazides are frlzation .tempFraturefS about E to 5 i those derived from mononuclear aromatic dibasic acids f i nines s out 3 g a P g onger such as terephthalic, isophthalic, and phthalic acids alas We or er peno f 6 eslre though polynuclear aromatic dibasic acids can be used Conventlonal Polymenzanon q pq known In the if desired art can be used for these polymerizations.

o f h l es of N,N'-bis(isomaleimide) pol Atmospheric pressures are preferred although superhydrazides of this invention are normally solid, linear, atmospherlq as Well as subatmospherlc PWSSUTCS can high polymers obtained by the condensation polymerizaused 1f deslredtion of equimolar amounts of N,N'-bis(isomaleimide and The P Y Y Of this ll'lYentlon can be dscrlbed dihydrazides in polar solvents. Schematically this may be generally as rlgld orp ous sollds capable of being cast indicated by the equation; 5 into useful films or drawn into useful fibers. Their physical O and mechanical properties fall in a range suitable for g y} structural or formed articles, self supporting films and O the like. These polyhydrazides also exhibit useful elec- CH 0 J & trical properties and stability to ultraviolet radiation. {1 0 0 U flHNNH NHNHI W The invention is further descrIbed by the examples solvent which follow. All parts and percentages are by weight unless otherwise specified.

3 EXAMPLES 1-8 Hydrazide syntheses The general synthesis of the dihydrazides used in this invention is described below.

A three-necked, two liter round bottom flask equipped with a stirrer, addition funnel, condenser and thermometer was charged with 175 g. (3.5 moles) of hydrazine hydrate and one liter of methanol. A solution of 0.5 mole of the dimethyl ester of one of the dibasic acids enumerated below in 250 ml. of methanol was added to the reaction flask through the addition funnel dropwise at a rate of about 1 to drops per second. Some of the esters afforded a solution, while others having limited solubility in methanol required that the reaction mixture be refluxed to effect solution. In either case once a homogeneous mixture was attained, it was allowed to stand overnight at ambient temperatures without stirring. The solid which precipitated out was removed by filtration, washed with methanol on the filter and dried in a vacuum oven at about 70 C. The resultant dihydrazides can be recrystallized from methanol-water. Acids subjected to this method include, oxalic, malonic, succinic, adipic, sebacic, terephthalic, isophthalic, phthalic acids. Yields, melting points, and temperatures of the hydrazides prepared are presented in Table I.

TABLE I.DIHYDRAZIDES TABLE I. Continued Formula of product 0 0 Conditions of Ex- Preparation ample H2NNH C-X-CI-INH 'I., Yield, M.1., C. No. where X is: Time, hr. percent obs.

0 R.1. (over- 00 300 night)- I I s Q .do 24 300 HT. is room temperature.

EXAMPLE 9 2 Copolymerization of dihydrazides and N,N'-bis (isomaleimide) The general method for the copolymerizations of N,N'- bis(isomaleimide) and polyhydrazides was as follows:

A three-necked 100 ml. flask equipped with a stirrer, thermometer and nitrogen inlet tube was charged with a solution of 0.01 mole of one of the dihydrazides prepared in Examples 1-8 in 50ml. of dry dimethyl sulfoxide. Then 0.01 mole of N,N'-bis(isomaleimide) was added under nitrogen with stirring. The reaction mixture showed a small exotherm. Stirring was continued overnight. The product N,N-bis(isomaleimide) polyhydrazide was isolated by pouring the reaction mixture-into an excess of water or acetone-ether mixture, filtering the precipitated polyhydrazide, and washing with either water or an acetone-ether mixture. The polyhydrazide was dried in a vacuum oven at 70 C.

TABLE II.SOLUTION POLYMERIZATION OF N,N-BIS(ISOMALEIMIDE) AND DIHYDRAZIDES R in the dihydrazide Polymerization conditions 0 O Temp. II II Temp, Time, Yield, C. Characteristics Example H2NHNC-RCNHN1I2 Solvent C. hr. Catalyst percent R.V. (about) of polymer (CH l 95 0. 13 155 Greenlish yellow so 1 (CH2)- l0-R.T. 21 99 0.2 140-180 Do. (CH2) R.T. 17 99 0. 29 140-180 D0. (CII2) -70 17 99 0. 22 140-180 D0. (OH2) O 22 84 0. 15 140-180 Do. -(CH D111SO/pyridine=1/1 .5-R.T. 17 Pyridine 99 0. 16 140-180 Yellow solid. 15 -(CH)Z) DMSO R.T. 70 .do 99 0.12 140-180 Greenlish yellow 16 (CH DMSO R11. 70 N N 99 0.09 140-180 Do- 17 (CH2)2- 22 99 0. 27 206 D0. 22 99 0. 23 220 Do. 68 0. 25 220 D0. 18 0. 58 230 Do. 18 l 85 0. 36 230 Yellow solid.

23 l 95 0. 10 245 Greenish yellow solid.

DMSO R.T. 19 I 94 0.30 230 Do.

HMPA 0-5 4 99 0. 15 230 Do.

DMAA 5 -25 14 l 99 0. 14 230 Do.

DMSO R.T. 65 5G 0. 05 218 Yellow solid.

1 Measured in dimethyl sult'oxide (Cone. 0,2 g./dl.) at 25 C. 2 Sample began to shrink, darken and decompose gradually. 3 Dimethyl suliozide.

4 Hexamethyl phosphoamide.

5 Dimethyl aeetamide.

The polyhydrazides prepared are listed in Table II together with pertinent physical data and the polymerization TABLE IV conditions used. 1511111111111 20 35 Tensile modulus (p.s.i.) 840,000 340,000 EXAMPLES 2736 e e st ength (pa-1.)" 4, 000 0,000 Elongation (percent) 5 1-7 Impact strength (ft.lbs./in. 30 Low temperature solution polymenzanon Tg. o.) 100 170 Giggle? permeaxhlllityt (cgJrnlillilfltim /24 thr./ The general procedure usedfor low temperature soluand 4.4 2.5 t1on polymenzation of N,N'-b1s(1s0male1m1de) d1hydraza ide adducts with a diacyl chloride was as follows: Dielectric commit,

A three-necked 100 ml. flask, equipped with a mechanlg cal stirrer, nitrogen inlet tube, drying tube, and thermom- 1x100 050165 eter was charged with 0.96 g. (0.005 mole) of N,N'-bis i gi g (isomaleimide), 0.01 mole of a dihydrazide and 20 ml. of 6: gi N,N-dimethylacetamide. This mixture was stirred at room 1X10 cycles temperature or with gentle heating, it required, until a 1 i ggz gszg s i i g zii g ggggi 83 :2 fggi g 2 Although the invention has been described in its pre- Ol43 g (0.01 mole) of finely divided lithium chloride ferred form with a certam amount of part1culanty, it is understood that the present d1sclosure has been made only parncles added w1th v1gorous st1rr1ng so that a umform by way of example, and that numerous changes can be suspens1on was formed. A solut1on of 0.005 mole of a d1- made Without de artin from the S irit and S60 e f the acyl chloride in 5 ml. of N,N'-dimethy1acetamide preinvention P g p p o cooled to about 0 to 50 C. was then introduced into Wh t l d the flask by means of a hypodermic syringe. An exotherm- 1 1S g' 1 ic reaction occurred immediately accompanied by a rapid P? y 1 g i i polyhydraincrease in the viscosity of the reaction mixture. The re- 2! es consls mg 0 um S represented y t e ormula' sultant polymer was isolated by pouring the reaction mix- 0 o 0 O o 0 o ture into either water or and acetonediethyl ether mixture F( g g g g H (1:1), filtration and washing with water in a Waring NHNH NHNHI INHNH ONHNH blendor. The polymer was then recovered and dried in a CH=OH H vacuum oven at about C.

The series of polyhydrazides thus prepared are delineated in Table III showing the reactants used, polymerization conditions, yields and some physical data.

TABLE III.-LOW TEMPERATURE SOLUTION POLYMEBIZATION OF THE N,N'BIS(ISOMALElMIDE)-DIHYDRAZINE ADDUCTS AND DIACYL CHLORIDE Yin the X in the dihydrazide diaoyl chloride Polymerization conditions 0 0 o 0 Time A]: E]; E II Temp., Time, Yield, C. Characteristics Example HNH X- NHNH O1 YCCl Solvent O. hr. percent R.V (about) of polymer 27 (o111 1 -(0H1)1- DMAA,LiCl -5--12 2 01 111501. 220 Yellow 5011a. 28 (CH2)a -(CH2)a DMAA,LiCl 5-10 1 Insol. 245 Grefiniish yellow 50 29 -(cH1)1 (c111)1- DMAA -5--10 1 03 111501. 245 Do. 30 (CH1) c111 1- HMPA 0 a 93 1115111. 245 o1e 1 1511 white :11 DMAA, 11101 -10 2% 90 0.111 2211 (1158111511 yellow 32 nMaamruso ropyl- -20 1% :90 0.22 225 Do.

I 33 DMAA,triethylene- -20 1% 04 0.19 2211 D0.

amine.

I I at Q- DMAA, pyridine -20 1% 01 0.11 225 Do.

as .--.do -12 a 90 0.36 280 Do.

as 1o -5 :1 0.39 280 Do.

a The medium contains equal molar amount of M01 as that of the acyl chloride group.

Measured in dimethyl sulfoxide solution (Cone. 0.2 g. d1.) at 25 C.

0 Sodium bicarbonate was added to neutralize the HCl during coagulation.

Polymer began to shrink, darken and decompose gradually. Dimethyl acetamide hexamethyl phosphoamide.

In order to demonstrate the areas of utility of the polyhydrazides of this invention further, physical property data as well as electrical and mechanical property data are presented in Table IV.

0 wherein each of R and R is a phenylene radical.

2. Polyhydrazide claimed in claim 1 wherein each of R and R is 3. Polyhydrazide claimed claim 1 wherein R is 3,144,435 8/ 1964 Saue is 26078 I 3,472,817 10/1969 Hedaya 26078 Q- and JOSEPH L. SCHOFER, Primary Examiner References Ci 5 C. A. HENDERSON, J 11., Assistant Examiner UNITED STATES PATENTS US. Cl. X.R.

3,041,376 6/1962 Sauers 260562 117-161; 26030.6 R, 30.8 DS, 32.6 N, 558 H, 561 H 

